KR101652217B1 - Reinforced Thermoplastic Resin Composition and Molded Article - Google Patents

Abstract

A graft copolymer obtained by polymerizing a monomer mixture comprising an aromatic alkenyl compound monomer (a) and a vinyl cyanide monomer (b) in the presence of 50 to 100% by weight of a polycarbonate resin (A) and a rubbery polymer (B1) B) 0 to 50% by weight of a main resin component (C); Glass fiber (D); A glycidyl ether unit-containing polymer (E) having a glycidyl ether unit and a mass average molecular weight of 3 800 to 60,000; Phosphate ester flame retardant (F); And an organic modified siloxane compound (G) at a specific ratio.

Description

 TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition,

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition reinforced by glass fibers and a molded article using the same.

(Thermoplastic resin composition, ABS resin, polycarbonate resin, ABS resin, etc.) or the thermoplastic resin composition (e.g., a thermoplastic resin composition) is used as a material of a case of a mobile device (a personal computer of a notebook and a tablet, a mobile phone including a smart phone, a digital camera, Is reinforced by an inorganic filler is widely used. As a method of manufacturing the case, a method of molding the thermoplastic resin composition by injection molding, which is generally capable of molding the shape to some extent, is adopted.

Recently, the case of a mobile device is required to be able to withstand the impact and load in a state of being thinner (slim), a bag or the like, and capable of being greaseless for the purpose of lowering the cost (However, Here, "grease-repellent" means that sufficient sliding property can be obtained without using grease (lubricant) by the self-lubricating property of the resin composition (SELF LUBRICATIVE) . ≪ / RTI > In order to satisfy such demands, the thermoplastic resin composition used in the case is required to have not only high rigidity and mechanical strength (impact resistance) but also high sliding property in the absence of grease and excellent moldability at the time of molding, when it is produced into a molded article.

However, the ABS resin, the polycarbonate resin and the ABS resin which are not reinforced by the inorganic filler have a low rigidity when they are made into finished articles, and thus can not meet the demand for slimming of the case.

When carbon fiber is used as the inorganic filler, it is possible to balance the rigidity and the mass when the article is made into a finished product. However, since the carbon fiber-reinforced thermoplastic resin composition has electromagnetic shielding properties, it can not be used in a wireless LAN type mobile device. Also, since the carbon fiber is black, it can not meet the demand for broad colorability.

In this respect, a glass fiber-reinforced thermoplastic resin composition has been studied as a thermoplastic resin composition used in a case.

The glass fiber-reinforced thermoplastic resin composition has high rigidity at the time of molding, and the case can be made slim. However, the glass fiber-reinforced thermoplastic resin composition has insufficient sliding properties and impact resistance at the time of molding.

As the thermoplastic resin composition capable of obtaining a molded article having excellent sliding properties, the following is proposed.

(1) A graft copolymer obtained by emulsion-polymerizing a monomer component in the presence of an aromatic polycarbonate resin and an ethylene-propylene-non-conjugated diene rubber-containing crosslinked latex and a hard copolymer comprising an aromatic vinyl monomer and a vinyl cyan monomer (Patent Document 1).

However, since the thermoplastic resin composition (1) has low rigidity at the time of molding, it can not cope with the demand for slimness of the case. In addition, the impact and mechanical strength of the finished product are low at one time, and the sliding property is also insufficient.

As the reinforced thermoplastic resin composition capable of obtaining a molded article having excellent mechanical strength, the following is proposed.

(2) A reinforced thermoplastic resin composition containing an aromatic polycarbonate resin, a graft copolymer, a glass fiber surface-treated with a water-soluble polyurethane, a glycidyl ether unit-containing polymer, and a phosphate ester flame retardant (Patent Document 2).

(3) A reinforced thermoplastic resin composition containing a polycarbonate resin, a rubber-containing polymer, and carbon fibers focused by an epoxy-based focusing agent (Patent Document 3).

However, the reinforced thermoplastic resin composition of (2) does not disclose a technique for improving the sliding property at the time of molding.

Further, since the reinforced thermoplastic resin composition (3) has electromagnetic shielding properties, it can not be used in a wireless LAN type mobile device, and since the carbon fiber is black, it can not meet the requirement for wide coloring property. And the like.

As the reinforced thermoplastic resin composition capable of obtaining a molded article having excellent surface appearance and sliding property, the following has been proposed.

(4) an aromatic polycarbonate resin, a thermoplastic resin such as a graft copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound to a diene rubber component, a copolymer comprising an aromatic vinyl compound and a vinyl cyanide compound, a reinforcing filler, an olefin wax , A reinforcing thermoplastic resin composition containing a lubricant such as a fluororesin, and a polyester elastomer (Patent Document 4).

However, the reinforced thermoplastic resin composition of (4) still has insufficient sliding properties at the time of molding.

There is proposed a reinforced thermoplastic resin composition to which an epoxy compound is added for the purpose of improving the sliding properties and the mechanical strength of a molded article in addition to the reinforced thermoplastic resin compositions of (1) to (4). However, a reinforced thermoplastic resin composition excellent in moldability and balance of the resulting molded article in terms of sliding property, rigidity, impact resistance, mechanical strength and surface appearance has not been proposed yet.

Patent Document 1: Japanese Patent No. 4915030 Patent Document 2: JP-A-2013-014747 Patent Document 3: Japanese Patent Application Laid-Open No. 60-88062 Patent Document 4: JP-A-10-306206

The present invention relates to a reinforced thermoplastic resin composition which is excellent in moldability, can attain simultaneously the improvement of the sliding property, the rigidity, the impact resistance and the mechanical strength to the resulting molded article, and can improve the surface appearance, , Impact resistance, mechanical strength and surface appearance.

The reinforced thermoplastic resin composition of the present invention comprises an aromatic alkenyl compound monomer (a) and a vinyl cyanide monomer (b) in the presence of 50 to 100% by weight of a polycarbonate resin (A) and a rubbery polymer (B1) (A) and the graft copolymer (B) is 100% by weight based on 100% by weight of the main resin component (C) comprising 0 to 50% by weight of the graft copolymer (B) obtained by polymerizing the monomer mixture ), Glass fiber (D), and glycidyl ether unit-containing polymer (E) having a glycidyl ether unit and having a mass average molecular weight of 3,800 to 60,000 (except for the graft copolymer (B) (C), a glass fiber (D), a glycidyl ether unit-containing polymer (A), a phosphoric acid ester-based flame retardant (F) and an organic modified siloxane compound E), a phosphate ester flame retardant (F), and an organic modified siloxane compound (G) Wherein the content of the glycidyl ether unit-containing polymer (E) is 1 to 10 parts by weight based on 100 parts by weight of the resin main component (C), and the phosphoric acid ester-based flame retardant ( F) is 1 to 30 parts by weight based on 100 parts by weight of the resin main component (C)

The content of the organic modified siloxane compound (G) is 1 to 5 parts by weight based on 100 parts by weight of the resin main component (C).

The molded article of the present invention is obtained by molding the reinforced thermoplastic resin composition of the present invention.

The reinforced thermoplastic resin composition of the present invention is excellent in moldability and can attain both the sliding property, the stiffness, the impact resistance and the mechanical strength of the obtained molded article at the same time, and the appearance of the surface can be improved.

The molded article of the present invention is excellent in rigidity, impact resistance and mechanical strength as well as in sliding properties, and has a good surface appearance.

The following definitions apply throughout this specification and claims.

"Constituent unit" means a unit derived from the monomer in which the monomer is formed by polymerization.

"Monomer" means a compound having a polymerizable unsaturated group.

The term "(meth) acrylate" means acrylate (acrylic acid ester) or methacrylate (methacrylic acid ester).

"Reinforced thermoplastic resin composition"

The reinforced thermoplastic resin composition of the present invention comprises a resin main component (C) containing a polycarbonate resin (A) as essential and containing a graft copolymer (B) as required; Glass fiber (D); A glycidyl ether unit-containing polymer (E); Phosphate ester flame retardant (F); Containing organic siloxane compound (G) as an essential component.

≪ Polycarbonate resin (A) >

The polycarbonate resin (A) is a resin obtained from a dihydroxydiaryl alkane and includes those branched (branched).

One kind of the polycarbonate resin (A) may be used alone, or two or more kinds thereof may be used in combination.

[Production method of polycarbonate resin (A)] [

The polycarbonate resin (A) is prepared by a known method. For example, by reacting a hydroxy or polyhydroxy compound with a phosgene or carbonic acid diester, or by melt polymerization. The dihydroxydialylalkane includes, for example, those having an alkyl group at the position of Ortho with respect to the hydroxyl group. Specific examples of the dihydroxydialylalkane include 4,4-dihydroxy 2,2-diphenylpropane (i.e., bisphenol A), tetramethyl bisphenol A, bis- (4-hydroxyphenyl) Isopropylbenzene and the like.

The branched polycarbonate resin (A) is prepared, for example, by replacing a part of the dihydroxy compound (for example, 0.2 to 2 mol%) with a polyhydroxy compound. Specific examples of the polyhydroxy compound include fluoroglycols, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 4,6-dimethyl- Tri- (4-hydroxyphenyl) -heptane, and 1,3,5-tri- (4-hydroxyphenyl) -benzene.

As the polycarbonate resin (A), those recycled as a compact disc or the like can be used.

[Viscosity-average molecular weight of polycarbonate resin (A)] [

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably from 15,000 to 35,000. When the viscosity average molecular weight of the polycarbonate resin (A) is 15,000 or more, the impact resistance of the molded article is further increased. When the viscosity average molecular weight of the polycarbonate resin (A) is 35,000 or less, the moldability of the reinforced thermoplastic resin composition is further increased. It is more preferable that the viscosity average molecular weight of the polycarbonate resin (A) is 17,000 to 25,000 because the mechanical strength, impact resistance and fluidity of the reinforced thermoplastic resin composition are particularly excellent.

The viscosity average molecular weight of the polycarbonate resin (A) can be determined, for example, by the solution viscosity method. When a commercially available polycarbonate resin (A) is used, a catalog value can be used.

[Ratio of polycarbonate resin (A)] [

The proportion of the polycarbonate resin (A) is 50 to 100% by weight, preferably 50 to 95% by weight, of the resin main component (C) (100% by weight). When the proportion of the polycarbonate resin (A) is 50% by weight or more, the impact resistance of the molded article is increased. If the ratio of the polycarbonate resin (A) is 95% by weight or less, the moldability of the reinforced thermoplastic resin composition becomes better.

≪ Graft Copolymer (B) >

The graft copolymer (B) is obtained by polymerizing a monomer mixture containing an aromatic alkenyl compound monomer (a) and a vinyl cyanide monomer (b) in the presence of a rubbery polymer (B1) (B2) having units of an alkenyl compound monomer (a) and a unit of a vinyl cyanide monomer (b) is grafted.

The graft copolymer (B) may be used alone or in combination of two or more.

[Rubbery polymer (B1)]

Examples of the rubbery polymer (B1) include rubbery polymers such as butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, acrylic rubber, (Hereinafter referred to as EPDM), epichlorohydrin rubber, diene-acrylic composite rubber, silicone (polysiloxane) -acryl composite rubber, EPDM-containing crosslinked latex and the like. Of these, preferred are butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, diene-acrylic composite rubber, silicone-acrylic composite rubber, EPDM and EPDM-containing crosslinked latex from the viewpoint of satisfactory plating performance Acrylate composite rubber is more preferable in that the molded article is excellent in flame retardancy and EPDM-containing crosslinked latex is more preferable because of good sliding property of the molded article.

The rubbery polymer (B1) is prepared, for example, by emulsion polymerization of a monomer forming the rubbery polymer (B1) in the presence of a radical polymerization initiator. According to the production method according to the emulsion polymerization method, it is easy to control the particle size of the rubbery polymer (B1).

The average particle diameter of the rubbery polymer (B1) (excluding the EPDM-containing crosslinked latex) is preferably 0.1 to 0.6 占 퐉 in that the impact resistance of the molded article is further increased.

The content of the rubbery polymer (B1) is preferably 0.5 to 3.5% by weight of the resin main component (C) (100% by weight). When the content of the rubbery polymer (B1) is 0.5% by weight or more, the impact resistance of the molded article is further increased. When the content of the rubbery polymer (B1) is 3.5% by weight or less, the moldability of the reinforced thermoplastic resin composition and the surface appearance of the molded article become better.

Diene-acrylic composite rubber:

The diene component of the diene-acrylic composite rubber contains 50% by weight or more of butadiene units. Examples of the diene component include butadiene rubber, styrene-butadiene rubber, and acrylonitrile-butadiene rubber.

The acrylic rubber component of the diene-acrylic composite rubber is obtained by polymerizing an alkyl (meth) acrylate (f) and a polyfunctional monomer (g).

Examples of the alkyl (meth) acrylate (f) include alkyl acrylates (such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate) (Hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate and the like). The alkyl (meth) acrylate (f) may be used singly or in combination of two or more.

Examples of the polyfunctional monomer (g) include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol Dimethacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. The polyfunctional monomer (g) may be used singly or in combination of two or more.

The composite structure of the diene-acrylic composite rubber includes a core shell structure in which the periphery of the diene component is covered with an acrylic rubber component; A core shell structure in which the periphery of the acrylic rubber component is covered with a diene component; A structure in which a diene component and an acrylic rubber component are entangled with each other; And a copolymer structure in which a diene monomer unit and an alkyl (meth) acrylate monomer unit are randomly arranged.

Silicone-acrylic composite rubber:

The silicone component of the silicone-acrylic composite rubber is based on a polyorganosiloxane. The silicone component is preferably a polyorganosiloxane containing a vinyl polymerizable functional group.

The acrylic rubber component of the silicone-acrylic composite rubber is the same as the acrylic rubber component of the diene-acrylic composite rubber.

The composite structure of the silicone-acrylic composite rubber includes a core shell structure in which the periphery of the silicon component is covered with an acrylic rubber component; A core shell structure in which the periphery of the acrylic rubber component is covered with a silicone component; A structure in which a silicon component and an acrylic rubber component are intertwined; A structure in which a segment of a polyorganosiloxane and a segment of a polyalkyl (meth) acrylate are linearly and three-dimensionally bonded to each other to form a mesh structure of a rubber structure.

EPDM-containing crosslinked latex:

The EPDM-containing crosslinked latex contains EPDM and an acid-modified low molecular weight? -Olefin copolymer.

EPDM is a copolymer composed of ethylene, propylene and a non-conjugated diene.

The ratio of ethylene units is preferably 80 to 90 mol% based on the total constituent units (100 mol%) of EPDM. When the ratio of the ethylene units is 80 mol% or more, compatibility with the acid-modified low-molecular-weight? -Olefin copolymer is improved, and the sliding property of the molded article is further enhanced. When the proportion of the ethylene unit is 90 mol% or less, the impact resistance of the molded article is further increased.

As the non-conjugated dienes, 1,4-hexadiene 5-ethylidene-2-norbornene, 5-vinylnorbornene, dicyclopentadiene and the like are preferable. The ratio of the non-conjugated diene units is preferably 0.1 to 2.0 mol% in the total constituent units (100 mol%) of the EPDM.

The proportion of the propylene unit is preferably the balance of the ethylene unit and the non-conjugated diene unit.

Examples of the acid-modified low molecular weight? -Olefin copolymer include acid-modified polyethylene composed of 99.8 to 80% by weight of? -Olefin units and 0.2 to 20% by weight of unsaturated carboxylic acid units.

Examples of the? -olefin include ethylene and the like.

Examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic acid monoamide.

The amount of the acid-modified low molecular weight? -Olefin copolymer is preferably 0.1 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of EPDM. When the amount of the acid-modified low-molecular-weight? -Olefin copolymer is 0.1 parts by weight or more, the sliding property of the molded article is further increased. And the moldability of the reinforced thermoplastic resin composition is further improved. When the amount of the acid-modified low molecular weight? -Olefin copolymer is 20 parts by weight or less, the sliding property of the molded article is further increased.

The gel content of the EPDM-containing crosslinked latex is preferably 40 to 98% by weight. When the gel content of the EPDM-containing crosslinked latex is 40% by weight or more, the surface appearance is better. When the gel content of the EPDM-containing crosslinked latex is 98% by weight or less, the impact resistance of the molded article is further increased.

The average particle diameter of the EPDM-containing crosslinked latex is preferably 0.2 to 1 占 퐉. When the average particle diameter of the EPDM-containing crosslinked latex is 0.2 m or more, the impact resistance of the molded article is further increased. When the average particle diameter of the EPDM-containing crosslinked latex is 1 μm or less, the surface appearance of the molded article becomes better.

[Molecular Chain (B2)]

The molecular chain (B2) has, as an optional component, an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide monomer (b) unit as essential components, and another monomer (c) copolymerizable therewith. The proportion of each monomer unit is preferably 50 to 90% by weight in terms of units of the aromatic alkenyl compound monomer (a) in view of excellent balance between the impact resistance of the molded article and the moldability of the reinforced thermoplastic resin composition, (b) units are preferably 10 to 50% by weight, and the proportion of other monomer (c) units is preferably 0 to 40% by weight (however, the total of monomers (a) to (c) .

Examples of the aromatic alkenyl compound monomer (a) include styrene,? -Methylstyrene, vinyltoluene, and the like, among which styrene is preferable.

Examples of the vinyl cyanide monomer (b) include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.

As the other monomer (c), alkyl methacrylate (methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, etc.), alkyl acrylate (methyl acrylate, ethyl acrylate, butyl acrylate, Maleimide compounds (such as N-phenylmaleimide) and the like.

[Acetone insoluble matter and acetone soluble fraction of graft copolymer (B)] [

The graft copolymer (B) contains 70 to 99% by weight of an acetone insoluble matter (insoluble matter) and is dissolved in an N, N-dimethylformamide solution of 0.2 g / dl of an acetone soluble fraction at 25 캜 The measured reduced viscosity is preferably 0.3 to 0.7 dl / g.

When the content of the acetone-insoluble matter is 70% by weight or more, the surface appearance of the molded article becomes better, and the moldability of the reinforced thermoplastic resin composition becomes better. When the content of insolubles in the acetone solvent is 99% by weight or less, the tear strength of the molded article is improved.

When the reduced viscosity of the acetone-soluble component is 0.3 dl / g or more, the tear strength of the molded product is improved. When the reduced viscosity of the acetone-soluble component is 0.7 dl / g or less, the surface appearance of the molded product becomes better, and the moldability of the reinforced thermoplastic resin composition becomes better.

The method of measuring acetone soluble fraction is as follows.

2.5 g of the graft copolymer is immersed in 90 ml of acetone, heated at 65 DEG C for 3 hours, and centrifuged at 1500 rpm for 30 minutes using a centrifuge. Thereafter, the supernatant is removed, and the remainder is dried in a vacuum drier at 65 ° C for 12 hours, dried, and then the sample is precisely weighed. The ratio (%) of the acetone soluble fraction of the graft copolymer in the mass difference (2.5 g - mass of the sample after drying) can be obtained. The reduced viscosity of the acetone-soluble fraction is measured at 25 ° C in a solution of N, N-dimethylformamide of 0.2 g / dl.

The acetone-soluble component is a polymer such as the molecular chain (B2) and a polymer not grafted on the rubbery polymer (B1). The acetone-soluble component is often produced simultaneously with the grafting of the molecular chain (B2) to the rubbery polymer (B1). Accordingly, the graft copolymer (B) includes an acetone-soluble fraction and an acetone-insoluble fraction.

[Process for producing graft copolymer (B)] [

The graft copolymer (B) can be obtained by graft-polymerizing the aromatic alkenyl compound monomer (a), the vinyl cyanide monomer (b) and, if necessary, the other monomer (c) in the presence of the rubbery polymer .

The graft polymerization method is preferably an emulsion polymerization method. In the graft polymerization, various chain transfer agents may be added to adjust the molecular weight of the graft copolymer (B), the grafting ratio, and the reduced viscosity of the acetone-soluble component.

When the rubbery polymer (B1) is an EPDM-containing crosslinked latex, the graft copolymer (B) is obtained by copolymerizing the aromatic alkenyl compound monomer (a) in the presence of, for example, 40 to 80% by weight of an EPDM- , A vinyl cyanide monomer (b) and, if necessary, another monomer (c), by emulsion graft polymerization.

When the proportion of the EPDM-containing crosslinked latex (as a solid component) is 40% by weight or more (the proportion of the monomer mixture is 60% by weight or less), the sliding property of the molded article is further enhanced. If the proportion of the EPDM-containing crosslinked latex (as a solid component) is 80% by weight or less (the proportion of the monomer mixture is 20% by weight or more), the surface appearance of the molded article becomes better.

[Ratio of graft copolymer (B)] [

The proportion of the graft copolymer (B) is 0 to 50% by weight, preferably 5 to 50% by weight, of the resin main component (C) (100% by weight). If the proportion of the graft copolymer (B) is 5% by weight or more, the moldability of the reinforced thermoplastic resin composition becomes better. When the proportion of the graft copolymer (B) is 50% by weight or less, the impact resistance of the molded article is increased.

≪ Glass fiber (D) >

The glass fiber (D) may be one of long fiber and short fiber. As the glass fiber (D), a short anisotropic short fiber is preferable, and a chopped fiber is more preferable.

The glass fiber (D) may be used singly or in combination of two or more kinds.

[Ratio between long diameter and short diameter]

The ratio of the major axis to the minor axis of the fiber cross section of the glass fiber (D) is preferably 1 or more, more preferably 1 to 6, and further preferably 2 to 4. When the long diameter / short diameter is 1 or more, the rigidity of the molded article is further increased. When the long diameter / short diameter is 6 or less, good parting (extrusion workability) is obtained.

The long fiber diameter / short diameter of the fiber cross section of the glass fiber (D) is obtained by observing the fiber cross section of the glass fiber (D) at eight places using an electron microscope and averaging the long diameter / short diameter at eight locations. At this time, the selection of 8 places appropriately selects the appropriate place to obtain the average. Extremely long fibers and extremely short fibers, for example, are excluded from observation as compared to others.

[Surface treatment agent]

The glass fiber (D) may be untreated glass fiber and may be surface treated with a surface treating agent.

Examples of the surface treatment agent include a coupling agent (for example, a silane coupling agent, a titanate coupling agent), a resin used for glass fiber coating or focusing, and the like.

Examples of the resin used for glass fiber coating or focusing include a thermoplastic resin (such as ethylene-vinyl acetate copolymer), a thermosetting resin (polyurethane resin, epoxy resin, and the like), and the molded article has higher impact resistance and mechanical strength. Water-soluble polyurethanes are more preferred. Water-soluble polyurethanes are polyurethanes that can be dissolved or dispersed in water. Examples of the water-soluble polyurethane include water-soluble polyurethanes known as a glass fiber sizing agent.

[Production method of glass fiber (D)] [

The glass fiber (D) can be obtained, for example, by surface-treating untreated glass fiber with a coupling agent or the like and surface-treating with water-soluble polyurethane.

[Ratio of glass fiber (D)] [

The ratio of the glass fiber (D) is 100% of the total of the resin main component (C), the glass fiber (D), the glycidyl ether unit-containing polymer (E), the phosphate ester flame retardant (F) and the organic modified siloxane compound (G) By weight, preferably 10 to 50% by weight, and more preferably 30 to 45% by weight. If the ratio of the glass fiber (D) is 10% by weight or more, the rigidity and the like of the molded product become high. When the proportion of the glass fiber (D) is 50% by weight or less, the moldability of the reinforced thermoplastic resin composition is improved.

≪ Glycidyl ether unit-containing polymer (E) >

The polymer (E) containing a glycidyl ether unit is a polymer having a glycidyl ether unit in the molecule. The glycidyl ether unit-containing polymer (E) does not include a block copolymer having a halogen atom such as bromine.

As the glycidyl ether unit-containing polymer (E), for example, a glycidyl ether type epoxy resin obtained by reaction of a compound having a hydroxy group with epichlorohydrin can be given.

Examples of the glycidyl ether type epoxy resin include bisphenol type epoxy resins; Novolak type epoxy resins; Polyglycidyl ethers of aliphatic polyhydric alcohols; And a biphenyl-type epoxy resin, those having a molecular chain having a repeating unit represented by the following formula (1) (for example, an epoxy group-containing phenoxy resin).

[Chemical Formula 1]

However, m is an integer of 1 or more.

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol A and bisphenol F epoxy resin.

Examples of the novolak-type epoxy resin include phenol novolac-type epoxy resin and cresol novolak-type epoxy resin.

Examples of the polyglycidyl ether of an aliphatic polyhydric alcohol include alkylene glycol diglycidyl ether (e.g., ethylene glycol diglycidyl ether and the like), polyoxyalkylene glycol diglycidyl ether ( For example, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc.), glycerin triglyceride Cidyl ether, and the like.

Examples of the glycidyl ether unit-containing polymer (E) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having a structure of bisphenol A and bisphenol F, phenol novolak type Epoxy resin, cresol novolak type epoxy resin and epoxy group-containing phenoxy resin are preferable.

The glycidyl ether unit-containing polymer (E) may be liquid at room temperature (20 캜), semi-solid state, or solid state. Solids are preferable considering the workability at the time of mixing and kneading.

The glycidyl ether type epoxy resin may be used singly or in combination of two or more kinds.

[Weight average molecular weight of polymer (E) containing glycidyl ether unit]

The weight average molecular weight of the glycidyl ether unit-containing polymer (E) is 3,800 to 60,000, preferably 5,500 to 50,000. When the weight average molecular weight of the glycidyl ether unit-containing polymer (E) is 3,800 or more, the impact resistance and mechanical strength of the molded article are increased. When the weight average molecular weight of the glycidyl ether unit-containing polymer (E) is 60,000 or less, the flame retardancy of the molded article is increased and the moldability of the reinforced thermoplastic resin composition is improved.

The mass average molecular weight of the glycidyl ether unit-containing polymer (E) can be determined, for example, by mass spectrometry. When the polymer (E) containing a commercial glycidyl ether unit is used, catalog values can be used.

[Method for obtaining the glycidyl ether unit-containing polymer (E)] [

Examples of commercial products of the glycidyl ether unit-containing polymer (E) include a jER (registered trademark) series manufactured by Mitsubishi Chemical Corporation, an Epototo (registered trademark) series manufactured by Sumitomo Metals, AER (registered trademark) series manufactured by Asahi Kasei Material Co., and Epikuron (registered trademark) series manufactured by DIC Corporation.

[Content of glycidyl ether unit-containing polymer (E)] [

The content of the glycidyl ether unit-containing polymer (E) is 1 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the resin main component (C). When the content of the glycidyl ether unit-containing polymer (E) is 1 part by weight or more, the mechanical strength and impact resistance of the molded article are increased. If the content of the glycidyl ether unit-containing polymer (E) is 10 parts by weight or less, the moldability of the reinforced thermoplastic resin composition becomes good and the flame retardancy of the molded article increases.

<Phosphoric acid ester flame retardant (F)>

The phosphate ester flame retardant (F) is a compound represented by the following formula (2).

(2)

However, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group and not all of R ¹ , R ² , R ³ and R ⁴ are simultaneously hydrogen atoms. P is 0 or 1, q is an integer of 1 or more, and r is an integer of 0 or more.

The organic group includes, for example, an optionally substituted alkyl group (e.g., methyl, ethyl, butyl, octyl), a cycloalkyl group (e.g., A phenyl group, an alkyl group, and a substituted phenyl group). The number of substituents when substituted is not limited. Examples of the substituted organic group include an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, and the like. (For example, an arylalkoxyalkyl group, etc.) in which such a substituent is bonded, or a group in which a substituent thereof is bonded by an oxygen atom, a nitrogen atom, a sulfur atom, or the like (for example, an arylsulfonylaryl group or the like).

The bivalent or higher organic group is a bivalent or higher functional group obtained by removing two or more hydrogen atoms bonded to the carbon atom in the organic group. For example, an alkylene group or a (substituted) phenylene group. The position of the hydrogen atom removed from the carbon atom is arbitrary.

Specific examples of the phosphate ester flame retardant (F) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, triclosyl phosphate, (Isopropylphenyl) phosphate, resorcinol diphenyl phosphate, polyphosphate (bisphenol A bisphosphate, hydroquinone bisphosphate, bisphenol A bisphosphate, bisphenol A bisphosphate, Bisphenol A bis (dicresylphosphate) phenylene bis (diphenylphosphate) phenylenebis (ditrylphosphate), phenylene bis (dicyclylphosphate), etc.) and the like .

The polyphosphate is obtained by dehydration condensation of various diol compounds such as polynuclear phenols (for example, bisphenol A and the like) with orthophosphoric acid. Examples of the diol substance include hydroquinone, resorcinol, phenylol methane, diphenylol dimethylmethane, dihydroxybiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene And the like.

As the phosphate ester flame retardant (F), trialkylsilyl phosphate, phenylene bis (diphenylphosphate) phenylenebis (dicylylphosphate) phenylenebis (ditrylphosphate) and bisphenol A bis (dicresylphosphate) are preferable , And phenylenebis (diphenylphosphate) phenylenebis (dicyclylphosphate) are more preferable.

The phosphate ester flame retardant (F) may be used singly or in combination of two or more.

The weight average molecular weight of the phosphate ester flame retardant (F) is preferably 326 or more, more preferably 326 or more, and still more preferably 550 or more. When the mass average molecular weight of the phosphate ester flame retardant (F) is 326 or more, the moldability of the reinforced thermoplastic resin composition becomes better and the surface appearance of the molded article becomes better. The mass average molecular weight of the phosphate ester flame retardant (F) is preferably 692 or less, more preferably 690 or less, and even more preferably 686 or less in terms of flame retardancy of the molded article.

The mass average molecular weight of the phosphate ester flame retardant (F) can be determined by mass spectrometry. Catalog values can be used when commercially available phosphate ester flame retardant (F) is used.

[Method for obtaining phosphate ester-based flame retardant (F)] [

Examples of the commercially available products of the phosphoric acid ester flame retardant (F) include FP series manufactured by ADEKA, Kronitex (registered trademark) series manufactured by Ajinomoto Fine Techno, Leohos (registered trademark) series manufactured by Chemchura Japan, CR series and PX series manufactured by Daihachi Chemical Co., Ltd., and the like.

[Phosphoric acid ester flame retardant (F) content]

The content of the phosphate ester flame retardant (F) is 1 to 30 parts by weight, preferably 3 to 23 parts by weight, based on 100 parts by weight of the resin main component (C). If the content of the phosphate ester flame retardant (F) is 1 part by weight or more, the moldability of the reinforced thermoplastic resin composition is improved. When the content of the phosphate ester flame retardant (F) is 30 parts by weight or less, the heat resistance and impact resistance of the molded article are increased.

&Lt; Organo-modified siloxane compound (G)

The organomodified siloxane compound (G) is a compound in which an organomodified siloxane and a thermoplastic resin are chemically bonded or a mixture of an organomodified siloxane and a thermoplastic resin.

The structure of the siloxane is not particularly limited. The method of organic modification of the siloxane is not particularly limited as long as it is a method of obtaining an organically modified siloxane capable of chemically bonding with a thermoplastic resin.

Examples of the thermoplastic resin include polyamide (nylon 6, nylon 66, etc.), polyolefin (polyethylene, polypropylene and the like), polyester (polyethylene terephthalate and polybutylene terephthalate), polycarbonate, polyamideimide, (Polystyrene, ABS resin, etc.), liquid crystal polyester copolymer (for example, acrylonitrile and styrene), polyphenylene oxide, polyphenylene oxide, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, Copolymers of nylon 6 and nylon 66), mixtures thereof (including alloys), and the like. As the thermoplastic resin, polyamide and polyolefin are preferable, and polyolefin is more preferable.

[Organically modified siloxane compound (G) content]

The content of the organic modified siloxane compound (G) is 1 to 5 parts by weight, preferably 2 to 4 parts by weight, based on 100 parts by weight of the resin main component (C). When the content of the organic modified siloxane compound (G) is 1 part by weight or more, the sliding property of the molded article is enhanced. When the content of the organomodified siloxane compound (G) is 5 parts by weight or less, deterioration of the impact resistance and mechanical strength of the molded article is suppressed.

<Other flame retardants>

The reinforced thermoplastic resin composition of the present invention can be used in combination with a phosphate ester flame retardant (F) in combination with a known non-halogen flame retardant in addition to the phosphate ester flame retardant (F). Examples of the non-halogen flame retardant include inorganic flame retardants such as pozzagene, polyester containing phosphorus, red phosphorus, and aluminum hydroxide.

As the flame-retardant flame retardant, those stabilized by being coated with a thermosetting resin or stabilized by being coated with a thermosetting resin and a metal hydroxide are used. Since the flame-retardant flame retardant alone has a flammability, it can be mixed with at least a part of the resin main component (C) or the polycarbonate resin (A) in advance to perform master batching.

&Lt; Flame retardant (H) >

The reinforced thermoplastic resin composition of the present invention may contain a flame retardant (H) for preventing dropping during combustion. Examples of the flame retardant include polytetrafluoroethylene, a compound having a tetrafluoroethylene unit, and a silicone-based polymer.

When a compound having polytetrafluoroethylene or a tetrafluoroethylene unit is blended as the flame retardant (H), the content of the flame retardant (H) is preferably 1 part by weight or more per 100 parts by weight of the resin component (C) Or less.

<Other ingredients>

The reinforced thermoplastic resin composition of the present invention may contain other modifiers, releasing agents, stabilizers for light or heat, antistatic agents, dyes, pigments and the like, if necessary.

&Lt; Process for producing reinforced thermoplastic resin composition >

The reinforced thermoplastic resin composition of the present invention comprises a polycarbonate resin (A), a graft copolymer (B), a glass fiber (D), a glycidyl ether unit-containing polymer (E), a phosphate ester flame retardant (F) , An organic modified siloxane compound (G) and other components as required. By mixing using a mixing device (for example, a Henschel mixer, a tumbler mixer, a NAUTA MIXER, or the like). And kneaded using a kneading apparatus (for example, a single screw extruder, a twin screw extruder, a Bumbary mixer, a Kneader, or the like).

&Lt; Action >

In the reinforced thermoplastic resin composition of the present invention described above, the polycarbonate resin (A) and the graft copolymer (B), the glass fiber (D), the glycidyl ether unit-containing polymer (E) The flame retardant (F), and the organic modified siloxane compound (G) at a specific ratio, and therefore the moldability is good and the rigidity, impact resistance and mechanical strength of the obtained molded article can be increased, can do.

<Molded article>

The molded article of the present invention is obtained by molding the reinforced thermoplastic resin composition of the present invention.

Examples of the molding method of the reinforced thermoplastic resin composition include an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a vacuum molding method, an air molding method, a calendar molding method, and an inflation molding method. Of these, an injection molding method and an injection compression molding method are preferable in that a molded product having excellent mass productivity and high dimensional accuracy can be obtained.

The molded article of the present invention can be used in various applications such as, for example, a personal computer (including a notebook computer and a tablet), a projector (including a liquid crystal projector), a television, a printer, a facsimile machine, (Including a mobile phone and a smart phone), a video camera (video), a musical instrument, a mobile device (an electronic organizer, a PDA), a lighting device, a communication device , Fishing, playground equipment (pachinko goods, etc.) vehicle products, furniture products, sanitary products, building materials products and the like. The present invention is particularly suitable for the case of a mobile device (a personal computer of a notebook computer and a tablet, a mobile device including a smart phone, etc.) in that the effect of the present invention is particularly remarkable.

Example

Hereinafter, specific examples will be described. The present invention is not limited to these embodiments. Quot; and &quot;% &quot; described below mean &quot; parts by weight &quot; and &quot;% by weight &quot;, respectively.

&Lt; Measurement method and evaluation method >

[Acetone soluble fraction]

2.5 g of the graft copolymer was immersed in 90 ml of acetone, heated at 65 DEG C for 3 hours, and centrifuged at 1500 rpm for 30 minutes using a centrifuge. Thereafter, the supernatant was removed, and the residue was dried in a vacuum drier at 65 DEG C for 12 hours, dried, and the sample was quenched. The ratio (%) of the acetone soluble fraction of the graft copolymer was obtained from the mass difference (2.5 g - mass of sample after drying). The reduced viscosity of acetone-soluble matter was measured at 25 캜 in a solution of 0.2 g / dl of N, N-dimethylformamide.

[Gel content]

The EPDM-containing crosslinked latex was coagulated in dilute sulfuric acid, the coagulated material was washed with water and dried to obtain a solid matter. 1 g of solid was taken and immersed in 200 ml of toluene for 40 hours. The resultant was filtered through a 200-mesh stainless steel wire mesh, and the residue was dried, and the gel content (%) was determined from the mass.

[Average particle diameter]

The average particle diameter of the EPDM-containing crosslinked latex was measured using a particle size distribution measuring device (product of Horiba, CAPA-500).

[Charpy impact strength]

The Charpy degree was measured according to ISO 179.

[Bending Strength and Bending Elastic Modulus]

Bending strength and bending elastic modulus were measured according to ISO 178. The bending strength and bending elastic modulus are indicators of the mechanical strength of the molded article.

[Fluxability (Coefficient of Friction)]

(Inner diameter: 20 mm, outer diameter: 25.6 mm) using an EM type friction tester (EFM-iii) according to JIS K 7218 method (ring on ring method) And the dynamic friction coefficient was measured by rubbing at a load of 4.0 kg and a test speed of 100 mm / sec.

[Surface appearance]

The molded article was visually observed and evaluated according to the following criteria.

○ (Good): There is no flow mark.

x (bad): Flow mark is recognized.

[Moldability]

The liquid crystal display cover (thickness: 1 mm) of the A4 size notebook was molded by an injection molding machine (J350E, 350 t equipped with an accumulator) at a molding temperature of 290 캜, an injection speed of 99%, a mold temperature of 85 Lt; 0 &gt; C. Moldability was evaluated according to the presence or absence of a short shot (uncharged portion) at the time of molding and whether or not a sink mark or gas was burned.

◎ (Excellent): No charge or sink mark and no gas.

○ (Good): Some sync marks were shown.

x (Bad): No trace of gas or gas was seen.

<Ingredients>

[Polycarbonate resin (A)]

Novarex (registered trademark) 7021PJ (viscosity average molecular weight (Mv): 18,800) manufactured by Mitsubishi Engineering Plastic Co., Ltd. was used as the polycarbonate resin (A-1).

[Preparation of graft copolymer (B-1)] [

A copolymer having an average particle diameter of 0.08 mu m composed of 85% of n-butyl acrylate units and 15% of methacrylate acid units in polybutadiene latex (solid content 100 parts) having a solid content concentration of 35% and an average particle diameter of 0.08 mu m Latex (2 parts as solids) was added with stirring. Stirring was continued for 30 minutes to obtain a rubbery polymer (B1-1) latex made of a non-expandable diene rubber having an average particle diameter of 0.28 mu m.

The rubber polymer (B1-1) latex was introduced into the reactor, and 100 parts of distilled water, 4 parts of wood rosin emulsifier, 0.4 part of Demol (registered trademark) N (product of Kao Corporation, naphthalenesulfonic acid formalin condensate) 0.04 parts of sodium, and 0.7 parts of dextrose were added. 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate and 0.06 part of sodium adititate were added to the mixture at the internal temperature of 60 占 폚, and then the mixture containing the following components was added over 90 minutes The mixture was continuously dripped and then held (kept) for 1 hour and cooled.

Acrylonitrile 30 parts

Styrene 70 parts

Cumene hydroperoxide 0.4 part &lt; RTI ID = 0.0 &gt;

1 part tert-Dodecyl mercaptan

The resultant graft copolymer (B-1) latex was solidified in diluted sulfuric acid, followed by washing, filtration and drying to obtain a dried powder of the graft copolymer (B-1).

The acetone-soluble fraction of the graft copolymer (B-1) was 27%. The reduced viscosity of the acetone-soluble fraction was 0.3 dl / g.

[Preparation of graft copolymer (B-2)] [

The raw materials were introduced into the reactor in the following proportions and polymerized while stirring under nitrogen substitution at 50 DEG C for 4 hours to obtain a rubbery polymer (B1-2) latex.

n-butyl acrylate 98 parts

1 part of 1,3-butylene glycol dimethacrylate

1 part of aryl methacrylate

Sodium dioctylsulfosuccinate 2.0 parts

Deionized water 300 parts

Potassium persulfate 0.3 part

Sodium Phosphate 12 Beard 0.5 part

Sodium Phosphate 12 Beard 0.3 part

The rubber polymer (B1-2) latex (100 parts as solid content) was introduced into another reactor, and 280 parts of ion exchange water was further added to dilute and the temperature was raised to 70 占 폚.

Separately, 0.7 part of benzoyl peroxide was dissolved in 100 parts of a monomer mixture composed of acrylonitrile / styrene = 29/71 (weight ratio) and replaced with nitrogen. The monomer mixture was added to the reactor containing the rubbery polymer (B1-2) latex at a rate of 30 parts / hour by metering pump. After all of the monomer mixture was added, the temperature of the reactor was raised to 80 캜 and stirring was continued for 30 minutes to obtain a graft copolymer (B-2) latex. The polymerization rate was 99%.

The graft copolymer (B-2) latex was added to the coagulation tank (coagulation tank) in which 0.15% aqueous solution of aluminum chloride (AlCl3 6 H2O) three times as much as the entire latex was introduced (90 deg. After the entire latex was added, the temperature in the coagulation bath was raised to 93 캜 and left as it was for 5 minutes. After cooling, the solution was decanted and washed with a centrifuge and dried to obtain a dried powder of the graft copolymer (B-2).

The acetone-soluble fraction of the graft copolymer (B-2) was 21%. The reduced viscosity of the acetone-soluble fraction was 0.70 dl / g.

[Preparation of graft copolymer (B-3)] [

(20 parts as solid content) having a solid content concentration of 35% and an average particle diameter of 0.08 탆 and a copolymer latex having an average particle diameter of 0.10 탆 composed of 82% of n-butyl acrylate units and 18% of methacrylate units 0.4 part as solid content) was added with stirring. Stirring was continued for 30 minutes to obtain a non-expandable diene rubber latex having an average particle diameter of 0.36 μm.

1 part of potassium nitrate, 150 parts of ion-exchanged water and a monomer mixture of the following composition were added to the reactor, and the inside temperature was raised to 50 占 폚 by substituting nitrogen.

n-butyl acrylate 80 parts

0.32 part of allyl methacrylate

0.16 part of ethylene glycol dimethacrylate

In the reactor, a solution prepared by dissolving 0.0002 part of ferrous sulfate, 0.0006 parts of disodium ethylenediaminetetraacetate, and 0.25 part of Rongalite was added to 10 parts of ion-exchanged water and reacted. The internal temperature at the end of the reaction was 75 ° C. The temperature was raised to 80 占 폚 and the reaction was continued for 1 hour to obtain a rubbery polymer (B1-3) comprising a non-conjugated diene rubber, a polybutyl acrylate rubber and a composite rubber. The polymerization rate was 98.8%.

A rubber polymer (B1-3) latex (50 parts as solid content) was introduced into the reactor, and 140 parts of ion-exchanged water was further diluted and heated to 70 캜.

Separately, 0.35 part of benzoyl peroxide was dissolved in 50 parts of a monomer mixture composed of acrylonitrile / styrene = 29/71 (weight ratio) and replaced with nitrogen. The monomer mixture was added to the reactor containing the rubbery polymer (B1-3) latex at a rate of 15 parts / hour by metering pump. After all of the monomer mixture was added, the temperature of the reactor was raised to 80 캜 and stirring was continued for 30 minutes to obtain a graft copolymer (B-3) latex. The polymerization rate was 99%.

The graft copolymer latex was added to a coagulation bath containing an aqueous solution (90 DEG C) containing 0.5% sulfuric acid three times as much as the entire latex while stirring to solidify. After the entire latex was added, the temperature in the coagulation bath was raised to 93 캜 and left as it was for 5 minutes. Cooled, desolvated and washed with a centrifuge, and dried to obtain a dried powder of the graft copolymer (B-3).

The acetone-soluble fraction of the graft copolymer (B-3) was 20%. The reduced viscosity of the acetone-soluble fraction was 0.7 dl / g.

[Preparation of graft copolymer (B-4)] [

96 parts of octamethyltetracyclosiloxane, 2 parts of? -Methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based compound. Then, 300 parts of distilled water dissolved with 0.67 part of sodium dodecylbenzenesulfonate was added thereto. The mixture was stirred at 10000 rpm for 2 minutes by a homomixer, and then subjected to a pre-mixing operation (once through operation) at a pressure of 30 MPa in a homogenizer Organosiloxane latex was obtained.

2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were poured into a reactor equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. The premixed organosiloxane latex was added dropwise over 4 hours while the aqueous solution was heated to 85 캜, and after the dropwise addition, the temperature was maintained for 1 hour and then cooled. The reaction solution was allowed to stand at room temperature for 48 hours, and neutralized with aqueous sodium hydroxide solution to obtain a polyorganosiloxane latex (L-1). A part of the polyorganosiloxane latex (L-1) was dried at 170 캜 for 30 minutes to obtain a solid content concentration of 17.3%.

119.5 parts of polyorganosiloxane latex (L-1) and 0.8 part of polyoxyethylene alkylphenyl ether sodium sulfate were introduced into a reactor equipped with a reagent injection vessel, a cooling tube, a jacket heater and a stirrer, and 203 parts of distilled water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tert-butyl hydroperoxide was added. The atmosphere was replaced with nitrogen by passing nitrogen stream through the reactor, and the temperature was raised to 60 캜. When the inside temperature of the reactor reached 60 占 폚, an aqueous solution in which 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediamine tetraacetate disodium salt and 0.24 part of Rongalite were dissolved in distilled water of 10 parts was added to initiate the radical polymerization. By polymerization of the acrylate component, the liquid temperature rose to 78 占 폚. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a rubbery polymer (B1-4) latex composed of a composite rubber of polyorganosiloxane and butyl acrylate rubber.

After the temperature of the liquid inside the reactor dropped to 60 캜, an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of distilled water was added. Subsequently, a mixed solution of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 parts of tetra-butyl hydroperoxide was added dropwise over about 1 hour to polymerize. After completion of the dropwise addition, the mixture was maintained for 1 hour, and then an aqueous solution prepared by dissolving 0.0002 part of ferrous sulfate, 0.0006 part of disodium ethylenediaminetetraacetate and 0.25 part of Rongalite in 10 parts of distilled water was added. Subsequently, a mixed solution of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of tetra-butyl hydroperoxide was added dropwise over about 40 minutes to polymerize. After completion of the dropwise addition, the mixture was kept for 1 hour and cooled to obtain a graft copolymer (B-4) latex.

150 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 5% was heated to 60 캜 and stirred. 100 parts of the graft copolymer (B-4) latex was gradually added dropwise into the calcium acetate aqueous solution and solidified. The obtained solidification product was separated, washed and dried to obtain a dried powder of the graft copolymer (B-4).

The acetone soluble fraction of the graft copolymer (B-4) was 26%. The reduced viscosity of the acetone-soluble fraction was 0.60 dl / g.

[Preparation of EPDM-containing crosslinked latex (a)] [

100 parts of EPDM (Mitsui Chemicals, EPT3012P, ratio of ethylene units: 82 mol%, ratio of nonconjugated diene (5-ethylidene-2-norbornene) units: 1 mol%) were dissolved in 566 parts of n-hexane, 10 parts of modified polyethylene (High Wax (registered trademark) 2203A, manufactured by Mitsui Chemicals, Inc.) was added, and 4.5 parts of oleic acid was added to dissolve completely. Separately, 0.5 part of ethylene glycol was added to an aqueous solution in which 0.9 part of potassium hydroxide was dissolved in 700 parts of water, and the mixture was maintained at 60 占 폚. The EPDM solution prepared above was gradually emulsified, followed by stirring with a homomixer. Subsequently, the solvent and a part of water were distilled to obtain a latex having an average particle diameter of 0.4 to 0.6 μm. To 100 parts of EPDM, 1.5 parts of divinylbenzene and 1.0 part of di-tert-butylperoxytrimethylcyclohexane were added to the latex. The mixture was reacted at 120 ° C for 1 hour to obtain an EPDM-containing crosslinked latex (a). The acid-denatured polyethylene content, gel content, and average particle diameter of the EPDM-containing crosslinked latex (a) are shown in Table 1.

[Preparation of EPDM-containing crosslinked latex (b)] [

(B) containing EPDM was obtained in the same manner as in the production of EPDM-containing crosslinked latex (a) except that 1.0 part of di-tert-butylperoxytrimethylcyclohexane was changed to 2.0 parts. The acid-denatured polyethylene content, gel content, and average particle diameter of the EPDM-containing crosslinked latex (b) are shown in Table 1.

[Preparation of EPDM-containing crosslinked latex (c)] [

Except that 1.0 part of di-tert-butylperoxytrimethylcyclohexane was changed to 3.0 parts, an EPDM-containing crosslinked latex (c) was obtained in the same manner as in the production of EPDM-containing crosslinked latex (a). The acid-denatured polyethylene content, gel content, and average particle diameter of the EPDM-containing crosslinked latex (c) are shown in Table 1.

[Preparation of EPDM-containing crosslinked latex (d)] [

The crosslinked latex (d) containing EPDM was obtained in the same manner as in the production of the EPDM-containing crosslinked latex (a) except that no acid-denatured polyethylene was added. The acid-denatured polyethylene content, gel content, and average particle diameter of the EPDM-containing crosslinked latex (d) are shown in Table 1.

[Preparation of EPDM-containing crosslinked latex (e)] [

An EPDM-containing crosslinked latex (e) was obtained in the same manner as in the production of the EPDM-containing crosslinked latex (a) except that 10 parts of the acid-denatured polyethylene was changed to 25 parts. The acid-denatured polyethylene content, gel content, and average particle diameter of the EPDM-containing crosslinked latex (e) are shown in Table 1.

[Preparation of graft copolymer (B-5)] [

70 parts of EPDM-containing crosslinked latex (a), 170 parts of water, 0.01 part of sodium hydroxide, 0.45 part of sodium pyrophosphate, 0.01 part of ferrous sulfate and 0.57 part of dextrose were placed in a stainless steel polymerization vessel equipped with a stirrer, 9 parts of acrylonitrile, 21 parts of styrene, and 1.0 part of cumene hydroperoxide were continuously added for 150 minutes at a constant temperature of 80 DEG C, and then 0.45 part of sodium pyrophosphate, 0.01 part of ferrous sulfate, 0.56 part of dextrose, 1.0 part of sodium and 30 parts of water were continuously added for 180 minutes to carry out polymerization to obtain a graft polymer (B-5) latex. The polymerization rate was 93%, and the precipitation amount of the coagulated material was 0.25%.

An antioxidant was added to the graft polymer (B-5) latex, which was solidified in sulfuric acid, washed, dehydrated and dried to obtain a graft copolymer (B-5) powder.

The acetone-soluble fraction of the graft copolymer (B-5) was 4%. The reduced viscosity of the acetone-soluble fraction was 0.30 dl / g.

[Preparation of Graft Copolymer (B-6)] [

A graft copolymer (B-6) latex was obtained in the same manner as in the production of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (b) was used instead of the EPDM containing crosslinked latex (a). The polymerization rate was 90%, and the amount of precipitation of the coagulated material was 0.22%.

A powder of the graft copolymer (B-6) was obtained in the same manner as in the production of the graft copolymer (B-5).

The acetone-soluble fraction of the graft copolymer (B-6) was 4%. The reduced viscosity of the acetone-soluble fraction was 0.29 dl / g.

[Preparation of graft copolymer (B-7)] [

A graft copolymer (B-7) latex was obtained in the same manner as in the production of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (c) was used instead of the EPDM containing crosslinked latex (a). The polymerization rate was 92%, and the precipitation amount of the coagulated material was 0.31%.

Further, a powder of the graft copolymer (B-7) was obtained in the same manner as in the production of the graft copolymer (B-5).

The acetone-soluble fraction of the graft copolymer (B-7) was 4%. The reduced viscosity of the acetone-soluble fraction was 0.30 dl / g.

[Preparation of graft copolymer (B-8)] [

A graft copolymer (B-8) latex was obtained in the same manner as in the production of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (d) was used instead of the EPDM-containing crosslinked latex (a). The polymerization rate was 92%, and the precipitation amount of the coagulated material was 0.52%.

A powder of the graft copolymer (B-8) was obtained in the same manner as in the production of the graft copolymer (B-5).

The acetone-soluble fraction of the graft copolymer (B-8) was 4%. The reduced viscosity of the acetone-soluble fraction was 0.29 dl / g.

[Preparation of graft copolymer (B-9)] [

A graft copolymer (B-9) latex was obtained in the same manner as in the production of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (a) was replaced with the EPDM containing crosslinked latex (e). The polymerization rate was 93%, and the precipitation amount of the coagulated material was 0.24%.

A powder of the graft copolymer (B-9) was obtained in the same manner as in the production of the graft copolymer (B-5).

The acetone soluble fraction of the graft copolymer (B-9) was 4%. The reduced viscosity of the acetone-soluble fraction was 0.29 dl / g.

[Glass fiber (D)]

As the glass fiber (D-1), a fiberglass fiber (product of Nitto Boweski, CSG 3PA-820, and surface treatment agent: water-soluble polyurethane, ratio of long diameter / short diameter: 4 was used.

As the glass fiber (D-2), glass fiber-clad fiber (CSH 3PA-870, product of Nitto Boweski, surface treatment agent: water-soluble polyurethane, ratio of long diameter / short diameter: 2 was used.

As the glass fiber (D-3), glass fiber-clad fiber (CS3PE-937 manufactured by Nitto Boweski, and surface treatment agent: water-soluble epoxy resin, ratio of long diameter / short diameter: 1) was used.

As the glass fiber (D-4), glass fiber-clad fiber (CS3PE-455 manufactured by Nitto Boweski and surface treatment agent: water-soluble polyurethane, ratio of long diameter / short diameter: 1) was used.

[Glycidyl ether unit-containing polymer (E)]

As the glycidyl ether unit-containing polymer (E-1), an epoxy group-containing phenoxy resin (JER (registered trademark) 4250, mass average molecular weight: 60,000) was used.

As the glycidyl ether unit-containing polymer (E-2), an epoxy group-containing phenoxy resin (JER (registered trademark) 1256, mass average molecular weight: 50,000, Mitsubishi Chemical Corporation) was used.

As the glycidyl ether unit-containing polymer (E-3), a bisphenol A type epoxy resin (JER (registered trademark) 1010, mass average molecular weight: 5,500, Mitsubishi Chemical Corporation) was used.

As the glycidyl ether unit-containing polymer (E-4), a bisphenol A type epoxy resin (JER (registered trademark) 1009, mass average molecular weight: 3,800, Mitsubishi Chemical Corporation) was used.

As the glycidyl ether unit-containing polymer (E-5), a bisphenol A type epoxy resin (JER (registered trademark) 1004, mass average molecular weight: 1,650, Mitsubishi Chemical Corporation) was used.

[Preparation of polymer (E-6) containing glycidyl ether unit]

82.42 parts of a bisphenol A type epoxy resin (epoxy equivalent: 467 g / eq) as a separable flask having a capacity of 500 ml and equipped with a stirrer, a thermometer, a nitrogen inlet and a cooling tube, and a bisphenol A liquid epoxy resin 6.3 parts of bisphenol A, 19.6 parts of p-cumylphenol, 7.5 parts of polyester resin (GV 335, acid value: 30 KOHmg / g, manufactured by Yupikaka Japan) And 30 parts of xylene were introduced, and the mixture was heated by heating in a nitrogen atmosphere.

When the internal temperature of the reaction system reached 80 캜, 0.18 part of a 5% aqueous lithium chloride solution was added and the temperature was raised. When the internal temperature of the reaction system reached 130 캜, the inside of the reaction system was decompressed to extract xylene and water to the outside. The reaction was carried out while maintaining the reaction temperature at 160 DEG C, and after 1 hour, nitrogen was introduced into the reaction system to return the pressure of the reaction system to normal pressure (constant pressure). 20.25 parts of a high molecular weight bisphenol A type epoxy resin (epoxy equivalent: 2,700 g / eq) was added at 7 hours after the reaction temperature reached 160 DEG C, and after stirring for 1 hour, a polyester resin (GV-730, acid value: 3 KOHmg / g, manufactured by YUPICA Corporation, Japan) were added and reacted at 180 占 폚 for 10 hours to obtain a high molecular weight epoxy resin. In order to provide the obtained high molecular weight epoxy resin for molecular weight measurement by GPC (Gel Permeation Chromatography), 0.1 g of the sample was dissolved in 10 ml of tetrahydrofuran, and as a result, about 0.05 g of the sample was not dissolved. After filtration with a filter paper (advantec 5c), the filtrate was used for molecular weight measurement by GPC. As a result, the mass average molecular weight was 70,200.

[Phosphoric acid ester flame retardant (F)]

As the phosphate ester flame retardant (F-1), phenylene bis (dicyclyl phosphate) (PX 200, product of Daihachi Chemical Co., Ltd., mass average molecular weight: 686, catalog value) was used.

As the phosphate ester flame retardant (F-2), phenylene bis (diphenylphosphate) (CR-733S, product of Daihachi Chemical Co., mass average molecular weight: 574, catalog value) was used.

As the phosphoric acid ester flame retardant (F-3), triphenyl phosphate (TPP, weight average molecular weight: 326, catalog value) was used.

As the phosphate ester flame retardant (F-4), bisphenol A biphenyl phosphate (BAPP manufactured by Ajinomoto Fine Techno Co., Ltd., mass average molecular weight: 692, catalog value) was used.

[Organically modified siloxane compound (G)]

As the organic modified siloxane compound (G-1), TEGOMER (registered trademark) AntiScratch 100 (compound of organic modified siloxane and polyolefin) manufactured by Evonik Industries was adopted.

As the organic modified siloxane compound (G-2), TEGOMER (registered trademark) AntiScratch 200 (compound of organic modified siloxane and polyamide) manufactured by Evonik Industries was adopted.

[Flame retardant (H)]

As the flame retardant (H-1), polytetrafluoroethylene (PTFE) was used.

[Other materials]

As the imparting agent other than the organomodified siloxane compound (G), the following compounds were used.

Silicone oil: Toray-Dow Corning products, SH-200-100CS.

Low molecular weight PTFE: L-5F, manufactured by Toray-Daikin Industries, Ltd.

Acid denatured polyethylene: product of Mitsui Chemicals, Inc., Hi-Wax (registered trademark) 2203A.

&Lt; Examples 1 to 25 and Comparative Examples 1 to 10 >

Each component was compounded so as to have the composition shown in Table 2, to obtain a reinforced thermoplastic resin composition, and a molded article for evaluation was obtained. The amounts of the components (E) to (H) and other components in the table are the amounts per 100 parts of the component (C). The moldability of the reinforced thermoplastic resin composition, the Charpy impact strength of the molded article, the flexural strength, the flexural modulus, the sliding property, and the appearance of the surface were evaluated. The evaluation results are shown in Table 2 and later.

Comparing Example 4 with Comparative Examples 1, 5, 6, and 7, the reinforced thermoplastic resin composition of the present invention is superior to the reinforced thermoplastic resin composition containing no organic modified siloxane compound (G) .

Comparing Example 5 with Comparative Example 2, the reinforced thermoplastic resin composition of the present invention is superior in impact resistance and mechanical strength to a molded product when compared with a reinforced thermoplastic resin composition containing no glycidyl ether unit-containing polymer (E) .

Comparing Example 5 with Comparative Example 3, the reinforced thermoplastic resin composition of the present invention is superior to the reinforced thermoplastic resin composition containing the glycidyl ether unit-containing polymer (E) having a weight average molecular weight lower than 3,800 The impact strength and the mechanical strength are excellent.

Comparing Example 5 and Comparative Example 4, the reinforced thermoplastic resin composition of the present invention is superior in moldability to a reinforced thermoplastic resin composition containing a glycidyl ether unit-containing polymer (E) having a weight average molecular weight of higher than 60,000 Able to know.

Comparing Example 5 with Comparative Example 8, the reinforced thermoplastic resin composition of the present invention is superior in impact resistance to a reinforced thermoplastic resin composition in which the proportion of the polycarbonate resin (A) in the main resin component (C) is less than 50% by weight Able to know.

Example 5 and Comparative Example 9 demonstrate that the reinforced thermoplastic resin composition of the present invention is superior in moldability to a reinforced thermoplastic resin composition having more than 10 parts of the glycidyl ether unit-containing polymer (E) per 100 parts of the main resin component (C) .

Comparing Example 5 and Comparative Example 10, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in moldability to a reinforced thermoplastic resin composition not containing the phosphate ester flame retardant (F).

The reinforced thermoplastic resin composition of the present invention is particularly useful as a material for a case of a mobile device (a notebook, a tablet, a mobile phone including a smart phone, a digital camera, a digital camcorder, and the like).

Claims (3)

A graft copolymer obtained by polymerizing a monomer mixture comprising an aromatic alkenyl compound monomer (a) and a vinyl cyanide monomer (b) in the presence of 50 to 100% by weight of a polycarbonate resin (A) and a rubbery polymer (B1) Wherein the total amount of the polycarbonate resin (A) and the graft copolymer (B) is 100% by weight, the resin main component (C) comprising 0 to 50%
Glass fibers (D),
A glycidyl ether unit-containing polymer (E) having a glycidyl ether unit and a weight average molecular weight of 3,800 to 60,000 (however, excluding the graft copolymer (B)),
Phosphate ester flame retardant (F), and
An organic modified siloxane compound (G) obtained by chemically bonding an organic modified siloxane with a polyamide or polyolefin or by mixing an organic modified siloxane with a polyamide or a polyolefin,
Lt; / RTI &gt;
The ratio of the glass fiber (D) to the glass fiber (D) is preferably in the range of 10 to 100 parts by weight based on 100 parts by weight of the resin main component (C), the glass fiber (D), the glycidyl ether unit containing polymer (E), the phosphoric acid ester flame retardant (F) Is 10 to 50% by weight in the total (100% by weight)
Wherein the content of the glycidyl ether unit-containing polymer (E) is 1 to 10 parts by weight based on 100 parts by weight of the resin main component (C)
The content of the phosphate ester flame retardant (F) is 1 to 30 parts by weight based on 100 parts by weight of the resin main component (C)
Wherein the content of the organic modified siloxane compound (G) is 1 to 5 parts by weight based on 100 parts by weight of the resin main component (C).
A molded article characterized in that the reinforced thermoplastic resin composition according to claim 1 is molded and processed.
The reinforced thermoplastic resin composition according to claim 1, further comprising a flame retardant auxiliary (H).